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AU743724B2 - Apparatus and method for sampling and IR-spectroscopic analysis of high-purity, hygroscopic liquids - Google Patents
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AU743724B2 - Apparatus and method for sampling and IR-spectroscopic analysis of high-purity, hygroscopic liquids - Google Patents

Apparatus and method for sampling and IR-spectroscopic analysis of high-purity, hygroscopic liquids Download PDF

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Publication number
AU743724B2
AU743724B2 AU89480/98A AU8948098A AU743724B2 AU 743724 B2 AU743724 B2 AU 743724B2 AU 89480/98 A AU89480/98 A AU 89480/98A AU 8948098 A AU8948098 A AU 8948098A AU 743724 B2 AU743724 B2 AU 743724B2
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AU
Australia
Prior art keywords
stainless steel
tap
steel tube
purity liquid
taps
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
AU89480/98A
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AU8948098A (en
Inventor
Klaus-Dieter Kreiger
Hartwig Rauleder
Lothar Zehe
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Evonik Operations GmbH
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Degussa GmbH
Degussa Huels AG
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Publication of AU8948098A publication Critical patent/AU8948098A/en
Assigned to DEGUSSA-HULS AKTIENGESELLSCHAFT reassignment DEGUSSA-HULS AKTIENGESELLSCHAFT Alteration of Name(s) of Applicant(s) under S113 Assignors: HULS INFRACOR GMBH
Application granted granted Critical
Publication of AU743724B2 publication Critical patent/AU743724B2/en
Assigned to DEGUSSA A.G. reassignment DEGUSSA A.G. Alteration of Name(s) of Applicant(s) under S113 Assignors: DEGUSSA-HULS AKTIENGESELLSCHAFT
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3577Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Optical Measuring Cells (AREA)

Description

4.
I
S F Ref: 432026
AUSTRALIA
PATENTS ACT 1990 COMPLETE SPECIRiCATIO FOR A STANDARD PATENT
ORIGINAL
Name and Address of Applicant: Actual Inventor(s): Address for Service: Invention Title: ~ulIi~~pcgIDmb Ir ~d T cF D-45764 Marl GERMAN*- ~'aY Hartwig Rauleder, Klaus-Dieter Kreiger and Lothar Zehe Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Apparatus and Method for Sampling and IR-spectroscopic Analysis of High-purity, Hygroscopic Liquids The following statement is a' full description of this invention, including the best method of performing it known to me/us:- 5845 Apparatus and Method for Sampling and IR-Spectroscopic Analysis of Highpurity Hygroscopic Liquids The present invention relates to an apparatus, its use and a process for the sampling and the quantitative, IR-spectroscopic determination of impurities in hygroscopic liquids having a purity of s more than 99.95% by weight.
High-purity products such as silicon tetrachloride are nowadays used, inter alia, in the production of optical fibres.
In the quality control of high-purity liquids, analytical methods employed should correctly reflect the actual purity of the product. Particularly during sampling, additional impurities can be introduced, for example moisture, which can also lead to secondary reactions.
It is known that impurities in silicon tetrachloride can be customarily determined quantitatively by IR spectroscopy, cf. Anal. Chem. 1987 59 1089-1093, and Anal. Chem. 1981 53 1967-1968.
It is also known that Teflon-coated cells or cells made of stainless steel together with Agel windows can be used in sampling and analysis in laboratories. However, it is found in practice that undesired impurities can be introduced before the actual measurement when using the known methods and cells on an industrial scale.
It is therefore an object of the present invention to provide an apparatus and also a practicable way of handling the apparatus for the industrial scale.
The invention provides an apparatus for the sampling and the quantitative, infra red spectroscopic determination of impurities in hygroscopic liquids, comprising: a stainless steel tube having a straight bore, a first end, and a second end; first flange attachment located at the first end and a second flange attachment located at the second end; cecil= a first calcium fluoride plate and a second calcium fluoride plate located at respective of said oil* 25 first end and said second end, said first and second calcium fluoride plates being oriented parallel to each other and perpendicular to the axis of the stainless steel tube; first and second outer flanges holding respective of the first and second calcium fluoride plates in place at the first and second ends of the tube, respectively, said first and second outer flanges being mechanically fixed to the first and second flange attachments, respectively; an at least one first seal separating the first plate from the first flange attachment and the first outer flange; an at least one second seal separating the second plate from the second flange attachment and the second outer flange; first and second three-way taps; a first stainless steel line coupling the first and second three-way taps; a second stainless steel line coupling the first three-way tap to the stainless steel tube; and a third stainless steel line coupling the second three-way tap to the stainless steel tube.
It is preferred that the stainless steel tube has an internal diameter of from 1 to 3cm and an internal length of from 5 to 20cm and the cell volume is from 5 to 140cm 3 and that the seal comprises a fluorinated polymer. In preferred embodiments of the invention, the calcium fluoride plate has a thickness of from 2 to 10Omm and a diameter of from 15 to 50 mm.
In another embodiment, the invention provides a method for preparing a high purity liquid for infra red analysis, comprising: filing a stainless steel tube of an apparatus with a high-purity liquid, said stainless steel tube partially defining a cell space and having a straight bore, a first end, and a second end; placing a first tap, a second tap, a third tap, and a fourth tap in a first configuration, said first tap being coupled to the stainless steel tube and to the second tap by a first line, said second tap being coupled to said stainless steel tube, said third tap being coupled to said first tap and a nitrogen source and a first outlet, said fourth tap being coupled to said second tap and a source for the high purity liquid and a second outlet; purging the first line with nitrogen gas by flowing nitrogen gas from the nitrogen gas source to the second outlet; reconfiguring the first, second, third, and fourth taps; flowing the high-purity liquid through the first line by flowing the high-purity liquid from the high purity liquid source to the first outlet; S"reconfiguring the first, second, and third taps; purging the cell space with the high-purity liquid by flowing the high purity liquid from the Shigh purity liquid source to the cell space; and performing an infra red spectroscopic measurement on a sample of the high purity liquid within the cell space.
It is preferred that a time of at least 1 hour elapses after the first step has been carried out and before the second step is carried out. In preferred embodiments, in the second step, purging with dry 2nitrogen is carried out for at least 0.1 hour, and in the fourth step, the purging of the cell space is 25 carried out such that at least 5 product changes, based on the volume of the cell, occur. In preferred embodiments of the invention, after carrying out the fourth step, taps are closed in the direction of the lines, taps are switched over, dry nitrogen is passed through the line in the direction of the outlet, the connection points are disconnected and the IR-spectroscopic measurement is subsequently carried out in a manner known per se.
It has surprisingly been found that an apparatus, cf. Fig. 1, comprising a stainless steel tube (1) having a straight bore at each end of which there is located a flange attachment comprising two mutually parallel calcium fluoride plates which are oriented perpendicular to the axis of the stainless steel tube and are each held in place by an annular outer flange where the respective flange parts 2a) are mechanically fixed to one another and at least one seal is provided in each case between the flange parts 2a) and the calcium fluoride plate and two three-way taps 6) which are connected to one another via a stainless steel line tap is connected to the stainless steel tube via the stainless steel line and tap is connected to the stainless steel tube via the stainless steel and tap is connected to the connection point (10) and tap is connected to R a connection point (13) is very suitable for reliable sampling and dependable, quantitative, IRspectroscopic determination of impurities in hygroscopic liquids having a purity of more than 99.95% by weight, in particular for high-purity silicon tetrachloride.
The present invention accordingly provides an apparatus for sampling and quantitative, IRspectroscopic determination of impurities in hygroscopic liquids having a purity of more than 99.95% by weight, which comprises a stainless steel tube having a straight bore at each end of which there is located a flange attachment comprising two mutually parallel calcium fluoride plates which are oriented perpendicular to the axis of the stainless steel tube and are each held in place by an annular outer flange where the respective flange parts 2a) are mechanically fixed to one another and at least one seal is provided in each case between the flange parts 2a) and the calcium fluoride plate and two three-way taps 6) which are connected to one another via a stainless steel line tap is connected to the stainless steel tube via the stainless steel line (8) and tap is connected to the stainless steel tube via the stainless steel and tap is connected to the connection point (10) and tap is connected to a connection point (13).
The figure schematically shows a preferred apparatus of the invention which is essentially connected via the connection points (10,13) to a dry nitrogen (12) supply and a plant section (16) from which the high-purity liquid to be analysed is taken.
*o
S
a ao• o*e •o Preferably, the stainless steelt tube of the apparatus of the invention has an internal diameter of from 1 to 3cm and an internal length of from 5 to 20cm and the cell volume (18).is from to 140cm 3 particularly preferably from 10 to 100cm 3 The stainless steels used here are appropriately corrosion-resistant, for example VA steels.
The apparatus of the invention also has calcium fluoride plates each preferably having a thickness of from 2 to 10 Onm and a diameter of from 15 to For the apparatus of the invention, use is appropriately made of seals comprising a fluorinated polymer, for example Viton seals, Kalrez seals.
The present invention also provides for the use of the apparatus of the 20 invention for the sampling and the quantitative, IR-spectroscopic determination of impurities 'in hygroscopic liquids, preferably high-purity silicon tetrachloride, having a purity of more than 99.95% by weight.
According to the invention, the sampling and the quantitative, IR-spectroscopic determination of impurities in high-purity liquids is generally carried out, cf. Figure, by in a first step, filling an apparatus S; according to the invention with high-purity liquid, preferably with high-purity silicon tetrachloride, and 15 closing the taps 6) in the direction of the lines then, appropriately after a time of at least 1 hour and preferably less than 24 hours has elapsed, in a second step, passing dry nitrogen (12) via tap connection point line connection point tap (14) and outlet with this nitrogen purge preferably being carried out for ai period! of from 0.1 to 12 hours, in a third step, after switching over the taps (141,14),, passing high-purity liquid,, preferably high-purity silicon tetrachloride, S. 20 from the plant section (16) via line tap (11) and outlet in a fourth step, after switching over the taps purging the cell space (18) with high-purity liquid via the taps (14, 6) and the lines (7, 8) in the direction of the outlet where at least five product changes, based on the volume of the cell, should appropriately be ensured and preference is given to from 10 to 30 product changes, and °i in a fifth step, after closing the taps 6) in the direction of the lines carrying out the IRspectroscopic measurement in a manner known per se.
On industrial plants, the method of the invention can advantageously be is carried out on the spot. However, it is also possible, after carrying out the fourth step, to close taps 6) in the direction of the lines switch over taps (11, 14), pass dry nitrogen (12) through line in the direction of the outlet disconnect the connection points (13,10) and subsequently carry out the IRspectroscopic measurement in a manner known per se.
The present invention therefore also provides a method of sampling and quantitative, IRspectroscopic determination of impurities in hygroscopic liquids having a purity of more than 99.95% by weight, which comprises in a first step, filling an apparatus according to the invention with highpurity liquid and closing the taps 6) in the direction of the lines in a second step, passing dry nitrogen (12) via tap connection point line connection point tap (14) and outlet in a third step, after switching over the taps (11,14), passing high-purity liquid from the plant section (16) via line tap (11) and outlet in a fourth step, after switching over the taps purging the cell space (18) with high-purity liquid via the taps (14, 6) and the lines 8) in the direction of the outlet (17) and in a fifth step, after closing the taps 6) in the direction of the lines (7, carrying out the IR-spectroscopic measurement in a manner known per se.
C04176 The apparatus of the invention and use of the method of the invention enables reliable quality assurance to be carried out for high-purity liquids, in particular for silicon tetrachloride, even in industrial plants.
The present invention is illustrated by the following examples without the scope of the invention being limited thereby.
Example For carrying out the sampling and the IR-spectroscopic analysis under conditions according to the invention, a cell whose design and construction corresponded to the description above (cf. Fig. 1) was assembled, filled with product (high-purity silicon tetrachloride) and allowed to stand for a number lo of hours. The sample material to be analysed was then passed through the cell so as to displace the cell contents; the volume of material in the cell was replaced at least five times. Finally, the cell was introduced into the sample space of a commercial infra-red spectrometer and measured in the range from 4000 to 1200cm-' at a resolution of 2cm- 1 see Fig. 2. Only harmonic vibrations of silicon o*o.
tetrachloride are observed in the spectrum. Virtually no bands of secondary components are 15 detectable.
Comparative Example To record the IR spectrum under standard sampling conditions, a new glass bottle which had been rinsed beforehand with product was filled with sample material to be analysed from the same product as above. Using a glass syringe which had likewise been rinsed beforehand with product, the sample 20 was taken from this bottle and introduced into a cell. The cell was made up of a cylindrical glass body with lateral ports, ground glass joints and stoppers and calcium fluoride windows at the ends of the two tube openings. After the filling procedure, the cell was measured under otherwise-identical measurement conditions in the same infra-red spectrometer as above, see Fig. 3.
To allow better comparison, the spectra were standardised to the same optical path lengths. In 25 Fig. 3, apart from the harmonic vibrations, additional bands occur: S. in the region of 3670cm- 1 the SiOH band, in the range from 2600 to 3100 cm- 1 the HCI bands, in the region of 2350 cm- 1 the 002 band.
These bands are caused, inter alia, by the sample handling. Their occurrence can be avoided by use of the apparatus of the invention and the method of the invention.
C04176

Claims (14)

1. An apparatus for the sampling and the quantitative, infra red spectroscopic determination of impurities in hygroscopic liquids, comprising: a stainless steel tube having a straight bore, a first end, and a second end; first flange attachment located at the first end and a second flange attachment located at the second end; a first calcium fluoride plate and a second calcium fluoride plate located at respective of said firstend and said second end, said first and second calcium fluoride plates being oriented parallel to each other and perpendicular to the axis of the stainless steel tube; first and second outer flanges holding respective of the first and second calcium fluoride plates in place at the first and second ends of the tube, respectively, said first and second outer flanges being mechanically fixed to the first and second flange attachments, respectively; an at least one first seal separating the first plate from the first flange attachment and the first outer flange; an at least one second seal separating the second plate from the second flange attachment and the second outer flange; first and second three-way taps; a first stainless steel line coupling the first and second three-waytaps; a second stainless steel line coupling the first three-way tap to the stainless steel tube; and ce.. 20 a third stainless steel line coupling the second three-way tap to the stainless steel tube.
2. An apparatus as claimed in claim 1, wherein the stainless steel tube has an internal diameter of from 1 to 3cm, an internal length of from 5 to 20cm and a cell volume of from 5 to 140cm 3
3. An apparatus as claimed in claim 1 or claim 2, wherein the first and second seals S• comprise a fluorinated polymer.
4. An apparatus as claimed in any one of claims 1 to 3, wherein the calcium fluoride plate has a thickness of from 2 to 10mm and a diameter of from 15 to 50 mm.
An apparatus for the sampling and the quantitative,.infra red spectroscopic determination "of impurities in hygroscopic liquids, said apparatus being substantially as hereinbefore described with reference to any one of the examples but excluding the comparative examples.
6. An apparatus for the sampling and the quantitative, infra red spectroscopic determination of impurities in hygroscopic liquids, said apparatus being substantially as hereinbefore described with reference to the accompanying drawings.
7. A method for preparing a high purity liquid for infra red analysis, comprising: filing a stainless steel tube of an apparatus with a high-purity liquid, said stainless steel tube partially defining a cell space and having a straight bore, a first end, and a second end; placing a first tap, a second tap, a third tap, and a f6urth tap in a first configuration, said first tap being coupled to the stainless steel tube and to the second tap by a first line, said second tap being coupled to said stainless steel tube, said third tap being coupled to said first tap and a nitrogen source and a first outlet, said fourth tap being coupled to said second tap and a source for.the high _7R 40 purity liquid and a second outlet; purging the first line with nitrogen gas by flowing nitrogen gas from the nitrogen gas source to the second outlet; reconfiguring the first, second, third, and fourth taps; flowing the high-purity liquid through the first line by flowing the high-purity liquid from the high purity liquid source to the first outlet; reconfiguring the first, second, and third taps; purging the cell space with the high-purity liquid by flowing the high purity liquid from the high purity liquid source to the cell space; and performing an infra red spectroscopic measurement on a sample of the high purity liquid within the cell space.
8. The method as claimed in claim 7, wherein at least one hour elapses after said step of filling the stainless steel tube and before said step of purging the first line with nitrogen gas.
9. The method as claimed in claim 7 or claim 8, wherein the step of purging the first line with nitrogen gas lasts continuously for at least 0.1 hour.
10. The method as claimed in any one of claims 7 to 9, wherein the step of purging the cell space is performed for a number of times based on the volume of the cell, said number being at least five.
11. The method as claimed in any one of claims 7 to 10, further comprising the steps of: closing the first and second taps in the direction of the stainless steel tube after the step l**S 20 of purging the cell space; flowing nitrogen gas from the nitrogen gas source to the second outlet; and *uncoupling the first and second taps from the third and fourth taps, respectively, before the step of performing the infra red spectroscopic measurement. a
12. The method of any one of claims 7 to 11, wherein the high purity liquid is a hygroscopic liquid having a purity of more than 99.95% by weight.
13. The method of claim 12, wherein the high purity liquid is silicon tetrachloride having a purity of more than 99.95% by weight.
14. A method for preparing a high purity liquid for infra red analysis, said method being i substantially as hereinbefore described with reference to any one of the examples but excluding the comparative examples. Dated 19 November, 2001 Degussa-Huils Aktiengesellschaft Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON
AU89480/98A 1997-10-23 1998-10-22 Apparatus and method for sampling and IR-spectroscopic analysis of high-purity, hygroscopic liquids Ceased AU743724B2 (en)

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DE19746862A DE19746862A1 (en) 1997-10-23 1997-10-23 Device and method for sampling and IR spectroscopic analysis of high-purity, hygroscopic liquids
DE19746862 1997-10-23

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US (1) US6142024A (en)
EP (1) EP0911625B1 (en)
JP (1) JP4268707B2 (en)
AU (1) AU743724B2 (en)
DE (2) DE19746862A1 (en)

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DE102005041137A1 (en) * 2005-08-30 2007-03-01 Degussa Ag Plasma reactor for cleaning silicon tetrachloride or germanium tetrachloride, comprises reactor housing, micro unit for plasma treatment, metallic heat exchanger, dielectric, perforated plate, lattice or network and high voltage electrode
DE102006003464A1 (en) * 2006-01-25 2007-07-26 Degussa Gmbh Method for producing a silicon layer on a substrate surface by vapor deposition
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DE59812849D1 (en) 2005-07-14
DE19746862A1 (en) 1999-04-29
EP0911625B1 (en) 2005-06-08
AU8948098A (en) 1999-05-13
JP4268707B2 (en) 2009-05-27
JPH11194077A (en) 1999-07-21
US6142024A (en) 2000-11-07
EP0911625A1 (en) 1999-04-28

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